Treating hydrocarbon oils



Sept-I 17, i935- c. F. TEICHMANN 2,014,915

TREATING HYDROCARBON OILS Filed Oct. 3, 1932 BY M /S. ATTORNEY Patented Sept. 17, 1935 l UNITED STATES 'rnEA'rnvG mnooAnBoN oILs Charles F. Teichmann, New York,v N. Y., assigner to The Texas Company, NewYork, N. Y., a corporation of Delaware Application October 3, 1932, Serial No. 635,945. 'n

claims. (c1. 19e- 19) This invention relates to the treatment of hydrocarbon oils and more particularly to the treatment of distillates obtained by cracking petroleum or other hydrocarbons which may A 5 contain'unstable, unsaturated compounds.

superatmospheric pressure, with a suitable contact catalyst whereby-a portion of the undesirable, unsaturated compounds are polymerized to compounds of higher boiling point, distilling the treated naphtha and contacting naphtha vapors with a suitable contact catalyst whereby any remaining undesirable, unsaturated compounds are polymerized. A product is thus obtained which is especially stable as to gum content and color. When hydrocarbons such as cracked naphtha and the like, containing certain types of unstable and undesirable, unsaturated compounds, ifor example, the diolenes, are contacted at elevated temperatures and in the liquid state with catalytic adsorbents which are active at such temperatures, a polymerization of the unstable, unsaturated compounds takes place. Such a polymerization results in the formation of new compounds known as polymers having boiling points higher than those of the original unsaturated compounds. This characteristic of the .polymers permits of their ready separation from the .treated naphtha by means of a distillation of the liquid treated productin which they are present. vSuch' liquid phase methods of treating cracked naphthamay be satisfactoryv for the treatment of most types of naphtha distillates. However,

in the case of some of the more highly unsaturated distillates produced by certain 'cracking conditions,I the products of a liquid treatment may be unstable when exposed to oxidation or' to long storage. 'Ihis instability may be due either to the presence of small quantities of undesirable; unsaturated compounds remaining in the oil or to partly polymerized compounds which have been formed during the liquid phase treat-'- ment. i y

It is appreciated that'by subjecting hydrocarbons containing unstable, unsaturated compoundsyto a treatmentinthe vapor phase with certain catalytic adsorbents, that a very complete separation of these unstable materials ls possible without in any way affecting those unsaturated compoundswhich, by their presence enhance the anti-detonating qualities' of the product. However, in the case of cracked naphthas containing large percentages of 'unsaturated compounds the vapor phase treatment may be uneconomic'al because of the large quantities 5j ,of polymers-which may be formed, quickly iilling up the pores oi the catalytic adsorbent material and rendering it useless until subjected to revivicatiom In accordance with my invention, the advantages of treating cracked naphtha both in the liquid and in the vapor phase are obtained yielding results not obtainable by the employment of either method alone. The liquid phase treatment serves as a vigorous means of removing 15'- the bulk of the unstable, unsaturated compounds.

Because of the higher pressures and higher temperaturesfemployed in this treatment the actual polymerization per unit weight of catalyst em- I ployed is high and the polymers which are formed 20 are continuously and concurrently washed out of the adsorbent by the associated portions of the naphtha. The vapor phase treatment which may be carried out at a somewhat lower pressure and temperature serves eiectively to yPolymerize'25l and separate any undesirable, unsaturated constituents which may not have been removed or which may have been formed during the liquid phase treatment.

Thus. bythe practice of the present invention, 30- cracked naphthas, derived from any type oi cracking process, and including those naphthas which are particularly refractory to ordinary .treating methods, can be purified and stabilized to yield motor fuel of a most satisfactory mer- 3 5- chantable quality.-

A particular advantage of the linvention lies in the fact that each of the two processes of treating may be worked at their highest eiciency without decreasing substantially the lives of the 4 0 adsorbents. 1

The invention will be fully understood from the following .description taken in connection with the drawing which represents in diagrammatic sectional elevation, an apparatus which may be 4.5v employed for carrying out the process.' 'Ihe apparatus illustrated in the drawing is shown and described merely for the purpose -ofaiding and understanding the process and it is to be underby the valve I2 with the inlet of the charge pump I3. This pump is connected through the line I4 and the valve I5 with the coils I6 of a suitable heater I1 which may be of any of the conventional types. The outlet of the heater coils is connected to the line I8, controlled by the valve I3, which enters the flash chamber 28.

" controlled by the automatic valve 28 which connects with the settling chamber 23. 'I'his settling chamber, which may with advantage be fitted with la conical bottom, is supplied with a liquid draw-off line 3| controlled by the valve 32 which leaves the structure at an upper point. The bottom of the settler is fitted with a line 33 controlled by the valve 34 which connects it with' the inlet of the pump 35. This pump discharges through the line 36 controlled by the valve 31 into the line I4.

The fractlonatlng tower 26 is fltted at a lower point of its structure with a steam spray 40 which is controlled by the valve 4I. At an upper point of the fractionating tower' there is situated the cooling coil 42 the purpose of which is to supply redux cooling for the fractionation. Immediately below the reilux cooling coil 42 there is fitted a trap tray 43 for facilitating the withdrawalof a certain portion of the reilux liquid.

At points intermediate the top and bottom of the tower 26 there are introduced the lines 44 and 45 controlled respectively by the valves 82 and 93, which serve a function which will be hereinafter described.

The uppermost point of the fractionating tower 26 communicates through the vapor line 41 controlled by the valve 48 with a lower point of the fractionating tower il. This fractionating tower is tted at a point near the bottom with a steam spray Elrcontrolled by the valve 52 and at an upper point with the cooling coil 53 for supplying reflux. The -bottom of the tower 50 is supplied with a draw-olf line 64 controlled by the valve 65 which leads to a suitable storage. The uppermost point `of the tower is provided with a vapor draw-olf line 66 fitted with a valve 61 which connects it with the coils 68 of the condenser 53. 'I'he outlet of this condenser communicates with the line 6Itted with the valve 62 which line enters the separatory chamber 63. The bottom of this separatory chamber is provided with a liquid draw-oil! line 64 controlled by the valve 66, which line communicates with a suitable storage tank (not shown) for the liquid product. The top of the separatory chamber is supplied with a vapor'draw-o line 66D controlled by the valve 61`which line connects the vapor space of the separator with a gas compression plant or a suitable gas storage.

The lines 44 and 4i which enter the fractionating and treating tower 26 at various levels are used for introducing into the tower a suspension of a catalytic adsorbent in a hydrocarbon oil.

-Thisslurryispreparedinthemixingchamber 83. Adsorbent catalyst which is stored in the storage tank 13 is introduced into the mixing chamber through the line 1I, controlled by the valve 12. Suitable hydrocarbons for preparing the catalytic adsorbent suspension are introduced into the mixing chamber through the supply line 13. To this supply line there are manifolded the lines 14, 15 and 16. These lines re- 5 spectively connect with the line 3|, the trap tray 43 and the discharge line 64 which leaves the separatory chamber 63. Each of these lines is tted with a control valve. These valves are respectively designated by the numerals 11, 18 10 and 13.

In order to bring about effective suspension of the catalyst adsorbent in hydrocarbon oilfa. gas spray 80 and the mechanical agitator 8| are provided. The gas spray is connected through 15 the line 82 controlled by the valve 83 with the vapor outlet of the separatory chamber 63.

'I'he bottom of the mixing chamber is provided with a draw-off line 84 controlled by the valve 85 which is vconnected to the inlet side of the 20 circulating pump 86. This pump discharges through the line 81 which is manifolded to the lines 44 and 45.

'I'he top of the mixing chamber is tted with aline 89 controlled by the valve 30, which leads 25 to the vapor line 66 at a point between the valve 61 and the discharge end.

In the operation of the process in connection with an apparatus such as that shown in the drawing, a cracked naphtha distillate which may 3o contain a varying percentage of hydrocarbons suitable for use as motor fuels is drawn from the naphtha storage tank III and delivered to the charge pump I3. This pump is of the high pressure type and is capable of delivering oil under 35 pressures of from 1000 to 2000 lbs. per sq. in. or more. Upon leaving the discharge side of this pump, the naphthal is mixed with a varying proportion of a slurry of partly spent catalytic adsorbent in hydrocarbon oil, which slurry is pro- 40 duced in a later stage of the process.

The mixture of naphtha and catalytic adsorbent; is delivered to the coils I6 of the heater I 1 where its temperature may be raised to a suitable working temperature which may be in the 45 range of from 400 to '100 F. Under the existing pressures, which may be the full working pressure of the charge pump I3, the naphtha is maintained substantially in the liquid phase.

During the heating operation which may be pro- 50 Ilonged by the use of a multiplicity of heating tubes, the undesirable, unsaturated compounds present in the naphtha distillate are caused to polymerize by the action of the catalytic adsorbent to form higher boiling hydrocarbons or 55 polymers.

Under certain conditions of operation it may be desirable to submit the untreated naphtha distillate to a preliminary stabilizing operation whereby low boiling hydrocarbons and non-condensable gases may be substantially removed. Such compounds, ii allowed to remain in the naphtha, tend to become adsorbed by the catalytic adsorbent and, in this manner, tend to reduce the polymerizing activity of the catalyst. The mixture of heated naphtha, polymers and catalytic adsorbent is delivered from the heater coll outlet through the valve I8 and passes into the flash drum 20. By the proper control of pressure within this flash drum, the hydrocarbons boiling within the distillation range of motor fuels are substantially vaporized while the higher boiling hydrocarbons which include the polymers remain in the liquid state. These liquid hydrocarbons or bottoms, together with the spent catl alytic adsorbent, accumulate at the vbottom of l adsorbentsthe hydrocarbons introduced therethrough the line 89 which connects with theA ture is maintained suflciently high to permit of into.

The catalytic adsorbents are introduced into an upper point ofw the tower in the form of a suspension which may be prepared by'admixing with the nely divided adsorbenta quantity of treated hydrocarbons which may or may not have been prepared by this process, or by suspending the adsorbents in an oil having a gravity duced through the line Il and the valve 'l2 intoA the mixing chamber 69 where it is agitated with oil taken off from the trap tray in an upper point of the fractionating tower 26, with the nal treated product withdrawn from the discharge line td from the separatory chamber 63 or with a heavier oil obtained from the top of the settling chamber 29. The operations incidental to the production of the last mentioned oil will be described hereinafter.

The formation of the suspension of catalytic adsorbent in hydrocarbon oil is advantageously brought about by agitating the mixture by means of an agitating device such as that indicated by the numeral 8l in the drawing. In certain operations of the process, the contents of the mixing chamber may be efciently agitated by introducing into the bottom of the chamber 69 hydrocarbon gases such as those produced in the process and which are separated from the nal treated condensate which accumulates in the separatory chamber 63. The gases are bubbled upwardly through thev mixture of adsorbent catalyst and oil and are drawn od from the top of the chamber vapor line connecting the vapor space of the separatory chamber with the gas compression plant or the storage for non-condensable gases.

The suspension of catalytic adsorbent in oil is charged by means of the pumpli into an upper point of th fractionating tower 26 through the line 8l and either line 44 or l5. The catalytic adsorbent and oil then pass downwardly through the tower whereby the ascending hydrocarbon vapors are brought into intimate contact with the adsorbent.

In the operation of the tower 26, the temperamaybe desirable to inject steam into the mixturev through the steam spray 4l.

The mixture of adsorbent and oil which collects at the bottom of the fractionating tower 25 is drawn oi through the line 21 controlled by the automatic valve 28 and pass into the settling chamber 29 where the mixture is allowed to 5 settle.

From an upper point of the settling chamber it is possible to withdraw o il which is almost entirely free from adsorbent. This oil may be drawn olf through the line 3i controlled by the l0 valve 32 and passes to a suitable storage tank.

A concentration of the partly spent adsorbent takes place at the bottom of the settling chamber and this adsorbent, together with a certain proportion of the oil, may be withdrawn from the l5 bottom of the settler in the form of a thick slurry. This slurry is drawn off at the bottom of the settler through the line 33 controlled by the valve 34 and is delivered to the suction side of the circulating pump 35 by which it is caused to 20 ow through the line 3d controlled by the valve 3l and to enter in the line' l@ at a point between the valve l5 and the inlet to the heater coil it.

The treated vapors which escape from the top of the tower 26 pass through the, vapor line dll 25 and the control valve t8 and enter a lower point of..the iractionating tower 5d. The purpose of the fractionating tower 5G isto remove all traces of polymers which may have been produced in the treating operation conducted in the tower 2d and 30 which may not have been removed. The vapors introduced into this tower pass upwardly in contact with av descending iiow of redux liquid and in this way there is produced a vapor fraction having the characteristics desired in the ill 35 motor fuel. These treated vapors are drawn ofi from the top of the tower through the vapor line 56 and the valve 5l and are delivered into the coil 58 of the condenser 59 where substantial con densation is brought about.

The pressure maintained within the fractionating tower 5t may vary from atmospheric to a -value only slightly less than that maintained in the tower 2t.

In those operations where, the vapor phase treatment in the tower 26 is carried out under substantial pressures, it may be desirable to carry out the condensation of the treated vapors under pressure. This is most advantageously carried out by proper manipulation of the valve 5l and 50 62 which control respectively the inlet and'outlet of the condenser coil 58 of the condenser 59. The condensate is delivered into the separatory chamber 63 where the pressure may be reduced in order to bring about the separation of noncondensable gases and light hydrocarbons which may have been dissolved in the condensate. These light hydrocarbons and non-condensable gases are drawn od through the line 56 controlled by the valve 6l and may be delivered to a gas compression plantA orr a storage for non-condensable gases. The liquid hydrocarbons `which accumulate at the bottom of the separatory chamber ow through the draw-od line 64 controlled by the automatic valve 65 to a storage tank not shown. t

In the operation of the herein disclosed process, it may be desirable to use adsorbent catalysts such as fullers earth or the like. It may be preherable, however, to usean adsorbent decolorizing 'm clay of the montmorillonite type which has been subjected to a treatment with acid and which exhibits its greatest eiilciency at temperatures in excess of 250 F. when used for decolorizing mirri--l eating oils. A material of this type is disclosed in the U. S. Patent No. 1,642,871, issued to Marvin L. Chappell, Richard F. Davis and Merle M. Moore.

Obviously many modiiications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. In the production of a color and gum stable motor fuel from a cracked naphtha distillate the steps which comprise heating the naphtha together with a partly spent catalytic adsorbent obtained from a subsequent operation to a temperature of between 400 to '700 F. while maintained substantially in the liquid phase by the use of pressures of from 1000 to 2000 pounds per square inch whereby a portion of the undesirable, unsaturated hydrocarbons is polymerized to higher boiling compounds, flashing the naphtha and fractionating the flashed vapors to produce Aa partly treated vapor fraction of a definite boiling range, passing this lfraction into a treating and rectifying apparatus wherein the vapors are simultaneously fractionated and contacted with a countercurrent flowing suspension of a catalytic Aadsorbent in a liquid hydrocarbon, maintaining.

the temperature sufficiently high to maintain in liquid form the hydrocarbons desired in the final product, withdrawing the treated fractionated hydrocarbon vapors and condensing them to yield a color stable motor fuel while simultaneously withdrawing unvaporized higher boiling hydrocarbons and partly spent catalytic adsorbent,

separating excess higher boiling hydrocarbons' from the adsorbent material and passing the latter to the rst step of the process.

2. In the production of a color and gum stable motor fuel from a cracked naphtha'distillate the steps which comprise heating the naphtha together with a partly spent acid treated adsorbent decolorizing earth obtained from a subsequent operation to a temperature of from 400 to r100 F. while maintained substantially in the liquid phase by the use of pressures of from 1000 to 2000 pounds per square inch whereby a portion of the undesirable, unsaturated hydrocarbons is polymerized to higher boiling compounds, hashing the naphtha and fractionating the flashed vapors to produce a partly treated vapor fraction of a definite boiling rangepassing this fraction into a treating and rectifying apparatus wherein the vapors are simultaneously fractionated and contacted with a countercurrent owing suspension of an acid treated adsorbent decolorizing earth in a liquid hydrocarbon, maintaining the temperature sufliciently high to maintain in vapor form the ble motor fuel while simultaneously withdrawing unvaporized higher boiling hydrocarbons and partly spent adsorbent material, separating excess higher boiling hydrocarbons from the adsorbent material and passing the latter to the first i step of the process.

3. The process of producing a color and gum stable motor fuel from a cracked naphtha distillate, which comprises subjecting the naphtha to contact with a partly spent solid adsorbent cata.

lytic material at a temperature above the normal vaporizing temperature of the naphtha but below an active cracking temperature and under a superatmospheric pressure suicient to prevent substantial v aporization of the naphtha, to effect a polymerization of undesirable unsaturated constituents of said naphtha to compounds of higher boiling point, dashing the treated naphtha to a lower pressure, fractionating the treated vapors to remove therefrom higher boiling hydrocarbons, subjecting the fractionated naphtha vapors to contact with relatively fresh solid catalytic adsorbent material while essentially in the vapor phase to effect a further polymerization of undesirable, unsaturated constituents, separating the treated vapors from the resultant higher boiling polymers, condensing the treated vapors and collecting them as a condensed treated liquid, withdrawing unvaporized oil and adsorbent from the fractionating stage, separating excess oil from the adsorbent material, subsequently employing the adsorbent material inthe first step of the process, and employing the excess oil for introducing adsorbent material into the vapor-phase treating stage.

4. The process of producing a color and gum stable motor fuel from a cracked naphtha distillate, which comprises subjecting the naphtha to contact with a partly spent solid adsorbent catalytic material at a temperature of from 400 to 700 F. and under a pressure of at least 1000 pounds per square inch to effect a polymerization of undesirable unsaturated constituents of said naphtha to compounds of higher boiling point, hashing the treated naphtha to a lower pres` sure, fractionating the treated vapors to remove therefrom higher boiling hydrocarbons, subjectf ing the remaining naphtha vapors to contact with relatively fresh solid catalytic adsorbent mate-- rial while essentially in the vapor phase to effect a further polymerization of undesirable, unsaturated constituents, separating the treated va-1 pors from the resultant higher boiling polymers, condensing the treated vapors and collecting them as a condensed treated liquid, and subse` quently employing the adsorbent material from the low pressure .treating stage in the high-presi sure treating stage.

5. The process of producing a color and gum stable motor fuel from a cracked naphtha distillate, which comprises heating the naphtha to an elevated temperature above the normal vaporizing temperature of the naphtha but below an active cracking temperature in the presence or partly spent solid catalytic adsorbent material and unf der high super-atmospheric pressure to effect a polymerization of undesirable unsaturated con-'- stituents of said naphtha to polymers of higher -boiling point, ashing the treated naphtha. to a lower pressure to separate vapors of the' desired treated naphtha from polymers that may be contained therein, passing the resultant vapors in countercurrent to a suspension of solid catalytic adsorbent material in hydrocarbon oil and vsimultaneously rectifying the vapors, withdrawing the treated vapors, condensing them and collecting them as a condensed treated liquid, separately collecting oil unvaporized in therectifying operation together with partly spent catalytic adsorbent material, separating excess unvaporized yoilfrom the adsorbent, and returning said partly spent catalytic adsorbent material to the'rst 70 

